Dynamics of Model lonomer Melts of Various Architectures

Ion-containing polymers have potential as single-ion conducting battery electrolyte materials. Their conductivity is often too low for such applications due to the low dielectric polymer backbone and resulting strong aggregation of ions. We simulate coarse-grained ionomer melts (with explicit counterions) of various polymer architectures to understand the effect of polymer connectivity on the dynamics. We report on the polymer and counterion dynamics as a function of periodically or randomly spaced charged groups, which can be placed in the backbone or pendant to it. The spacer length is also varied. The simulations reveal the mechanism of ion transport, the coupling between counterion and polymer dynamics, and the dependence of the ion dynamics on polymer architecture. Within the ionic aggregrates, ion dynamics is rather fluid and relatively fast. The larger scale dynamics (time and length) depends strongly on the large scale morphology of the ionomer. Systems with percolated clusters have faster counterion diffusion than systems with isolated clusters. In the systems with isolated clusters counterions diffuse through the combination, rearrangement, and separation of neighboring clusters. In this process, counterions move from one cluster to another without ever being separated from a cluster. In percolated systems, the counterions can move similarly without the need for the merging of clusters. Thus, the ion diffusion does not involve a hopping process. The dynamics also depends significantly on the details of the polymer architecture beyond the aggregate morphology. Adding randomness in spacing of the charges can either increase or decrease the ion diffusion, depending on the specific type of random sequence.